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超臨界流體 萃取 , 層析及其他應用

超臨界流體 萃取 , 層析及其他應用. Supercritical Fluid Extraction, Chromatography and Other Applications 林華經 引光生物科技有限公司. What is a Supercritical Fluid ?.

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超臨界流體 萃取 , 層析及其他應用

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  1. 超臨界流體萃取,層析及其他應用 Supercritical Fluid Extraction, Chromatography and Other Applications 林華經 引光生物科技有限公司

  2. What is a Supercritical Fluid ? When the pressure and temperature of a substance is raised above its critical pressure and critical temperature (the critical point) the substance enters the supercritical state. A Supercritical Fluid is a substance with both gas- and liquid-like properties.

  3. Critical Temperature and Pressure • The Critical Temperature (Tc) is the maximum temperature at which a gas can be converted to a liquid by increasing the pressure. • The Critical Pressure (Pc) is the maximum pressure at which a liquid can be converted to a gas by increasing the temperature.

  4. SupercriticalFluid Liquid Solid Pressure Critical Point 31.3 oC, 1072 psi Triple Point Temperature Phase Diagram of Carbon Dioxide Gas

  5. Physical Properties of CO2

  6. Advantages of Supercritical Fluids as solvents • Solvating power related to density (at constant T) • Gas-like mass transport properties • Facile penetration into porous material

  7. -1 T (°C) P (atm)  (g mL ) c c c CO 31.3 72.9 0.47 2 N O 36.5 72.5 0.45 2 SF 45.5 37.1 0.74 2 NH 132.5 112.5 0.24 3 H O 374 227 0.34 2 n-C H 152 37.5 0.23 4 10 n-C H 197 33.3 0.23 6 12 Xe 16.6 58.4 1.10 CCl F 112 40.7 0.56 2 2 CHF 25.9 46.9 0.52 3 Critical Parameters of Common Fluids Source: “SFE and Its use in Chromatographic Sample Preparation” Ed. S. Westwood. Chapter 1

  8. Advantages of CO2 for SFE • Low critical parameters • Inert, Non-toxic, Nonflammable, Non-corrosive • Easily purified (inexpensive) • Nonpolar: dielectric constant similar to hexane • Modifiers can be used to increase polarity

  9. Supercritical Fluid Extraction (SFE) Basic Theory

  10. sample cell in heated chamber CO2 Pump (high pressure) Modifier Pump CO 2 CO 2 Trap Solid or Liquid SFE System Components Liquid Carbon Dioxide (requires a dip tube) Restrictor

  11. Advantages of SFE over Solvent Extraction • Faster • Results in minutes rather than hours • Selectivity results in cleaner extracts • Low Critical Parameters • Handling of thermally labile analytes • Non-hazardous solvents • Automated • Cost per test is lower • Limited or no solvent removal required • No solvent disposal costs

  12. The Mechanism of SFE A Three Step Process • Dissolving/Resolving analyte(s) 2. Sweeping the analyte(s) from the matrix 3. Trapping the analyte(s)

  13. SFE Mechanism SC-CO2 diffuses matrix, dissolves and resolves analyte from the matrix SC-CO2 + dissolved analyte to the trap High Pressure Liquid CO2 Heat

  14. Trapping Gaseous CO2 Gaseous CO2 • Trapping Solid • High Surface Area • Adequate Amount • Trapping Liquid • High Surface Tension • Analyte is Soluble • Low Volatility • Pressurized • Cryogenically Cooled • CO2 is changing • from a SF (2 ml/min) • to an expanded gas • (1 L/min) • Analyte no longer • soluble • Mechanical movement • of analyte due to the • rapid expansion requires • the use of trapping • material

  15. SFE - Method Development • Pressure • Increase pressure increases density = increase in solubilizing power. • Temperature • Increase temperature may decreases density = decrease in solubilizing power (ie CO2 at 100 bar) • Extraction Time • Flow Rate • Fluid Composition • Co-solvents/modifiers • Reactant Additive • Static vs. Dynamic Extraction

  16. Why Use Modifiers?Analytes that have polar components require the use of a co-solvent Triglycerides Phospholipids CH2OCOR1 R2COOCH CH2OCOR3 CH2OCOR1 R2COOCH O CH2OPOR3 O- R 1, 2 & 3 groups are long chain hydrocarbons (nonpolar) R 1 & 2 groups are long chain hydrocarbons (nonpolar), while R 3 contains phosphorus and nitrogen and is polar

  17. Modifiers (Co-solvents) in SFE Role of Modifiers in SFE Changes in Solvent Polarity • Interaction with Matrix • Interaction with Analyte Methods of Addition • Directly into extraction cell (spiking) • On line modifier addition (uses a second pump)

  18. SFE vs. Traditional Sample Extraction Methods Conclusion • SFE can be versatile, selective and faster • SFE reduces hazardous solvent use and cost • SFE can produce cleaner, more concentrated extracts for post extraction analysis

  19. Analyst’s Time Allotment

  20. Routine and Novel Applications of Analytical SFE

  21. SFE for Research

  22. Matrices Soil Tissue Clay Sandy Loam Sludge River Sediment Marine Sediment Fly Ash Incinerator Ash Target Analytes TPH PAH PCBs Pesticides Dibenzofurans Dioxins Environmental SFE Applications

  23. Approved Methods Environmental • US EPA 3560 - TPH in Soil: Supercritical Fluid Extraction of Total Recoverable Petroleum Hydrocarbons • US EPA 3561 - PAH in Soil: Supercritical Fluid Extraction of Polyaromatic Hydrocarbons • US EPA 3562 - PCB and OCP: Supercritical Fluid Extraction of Polychlorinated Biphenyls (PCBs) and Organochlorine • US EPA 3545: Pressurized Fluid Extraction (PFE) • USDOE STD-3013-99: Determination of Residual Water in Impure Plutonium Oxides • AOAC draft: SFE-GC/MS determination of pesticide residues in non-fatty fruits and vegetables

  24. Pharmaceutical/Natural Product Applications

  25. SFE of Natural Products -- Roger M. Smith LC-GC International, Jan. 1996, 9-15

  26. Microbial Natural ProductsR. M. Smith, op. cit.

  27. Extracts from BiomassR. M. Smith, op. cit.

  28. Summary R. M. Smith, op. cit. • Extracts typically cleaner than those obtained with organic solvents. • Mild conditions minimize degradation. • SFE methods are faster than organic solvent extractions.

  29. Extraction of Pharmaceuticals Using Pressurized Carbon DioxideJ. R. Dean, S. Khundker, J. Pharm. & Biomed. Anal, 15 (1997) 875-886 • Recoveries from 81% - 95+% • CO2 and CO2 with modifiers • Generally faster than other methods with better selectivity for target analytes. • Preconcentration steps could be eliminated in some cases. • Liquid matrices required immobilization on solid support or SPE cartridge.

  30. Animal Feeds J. R. Dean, S. Khundker, op. cit.

  31. FormulationsJ. R. Dean, S. Khundker, op. cit.

  32. Biological MatricesJ. R. Dean, S. Khundker, op. cit.

  33. MiscellaneousJ. R. Dean, S. Khundker, op. cit.

  34. Natural Materials StudiedM. J. Noh, et. al., op. cit.

  35. Natural Materials Studied, contd.M. J. Noh, et. al., op. cit.

  36. SummaryM. J. Noh, et. al., op. cit • For many materials, SFE yielded extracts with higher bioactivity than LSE. • SFE was found to be more selective than LSE for target compounds. • SFE conditions could be optimized to produce maximum levels of bioactivity.

  37. Drug Residues

  38. Study Summary • Compared to a conventional SPE method, the SFE method was more efficient and gave cleaner extracts with recoveries above 80% • K.S. Scott, J.S. Oliver, J. Anal.Toxicol. 21 (1997) 297.

  39. Supercritical Fluid Chromatography • SFC is a separation technique similar to HPLC and GC where the mobile phase or carrier gas is replaced by a supercritical fluid

  40. Limitations of GC and HPLC GC Sample Limitations : Volatility Thermal stability Low molecular weight HPLC Analytical Limitations : No universal detector Low efficiency Low resolution

  41. SFCOvercomes Limitations of GC and HPLC • Extends molecular weight range of GC • Lower operating temperature than GC • Faster separation time than HPLC • Higher separation efficiency than HPLC • Universal detector can be used, FID • Both packed (HPLC-type) and GC-type columns can be used

  42. Carbon Dioxide, CO2has desirable properties as a SFC solvent • Inexpensive • Highly pure • Very low UV absorbance • NO FID background noise • Low critical pressure and temperature • Non-toxic • Supercritical CO2 behaves as a nonpolar solvent such as heptane • Polar organic modifiers can be mixed with CO2 for more polar samples

  43. SFC Applications Industrial : • Synthetic oligomers, polymers / additives • Surfactants (polyglycols) • Oligo / polysaccharides, sucrose polyesters • Pesticides • Isocyanates • Dyes • Waxes

  44. SFC Applications Biochemical : • Steroids • Prostaglandins • Fatty acids / lipids • Antibiotics • Drugs of abuse

  45. SFC Applications Fossil Fuels : • Fractionation of petroleum and coal-derived fluids • Hydrocarbon group analysis • Simulated distillation

  46. Other Applications of Supercritical Fluid • Supercritical Fluid Cleaning • Supercritical Fluid Drying • Supercritical Fluid Reactions • Micro Particles Formation • Supercritical Water Oxidation System • Others

  47. Applications of Supercritical Fluid Technologies in Taiwan • IN THE PAST

  48. Applications of Supercritical Fluid Technologies in Taiwan • AT PRESENT

  49. Applications of Supercritical Fluid Technologies in Taiwan • IN THE FUTURE

  50. Thanks For Your Attention ! • 林華經 • 國立清華大學化工系學士 • 國立清華大學生科所碩士 • 國立清華大學化工系博士班 • 友翔實業股份有限公司 儀器部經理 • 引光生物科技有限公司 研發部經理

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